Alkyd resinous composition



g mown as falkyd tion products Patented i3, ligltie Frithjofi Zwilgmeyer, to National Inc, New York, York No Drawing.

Hamburg, N. e and Chemical Company, N..'Y., a corporation or New Application 1, gnor lgpril 18,. 1930 Serial No. 445,5 9

This invention relates to compositions of the class of resinous condensation products derived from an organic polycarboxylic acid and a polyhydric alcohol, which products have come to be resins or resins oi the Glyptal An object ofthe present invention is the prep- 4 aration or new resinous condensation products.

invention is the.

Another object of the present preparation of resinous condensation products derived from a polyhydric alcohol, an organic polycarboxylic acid, and an ester of an organic polycarboxylic acid which contains a free carboxyl group.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the new products as well as the several steps and the relation or one or more of such steps with respect to each of the others thereof employed for the preparation of such products which will be exemplifled in the products and process hereinafter disclosed. The scope of the invention will be indicated in the claims.

Resinous materialsof widely different properties have heretofore been made by the partial esterification of a polyhydric alcohol with an organic polycarboxylic acid to form an intermediate product containing unesterified hydroxyl groups followed by further condensation of the intermediate product with an organic monoor polycarboxylic acid. (Cf. U. S. Patents 1,098,776 and 1,098,777).

According to the present invention, synthetic resinous condensation products may be prepared from a partially esterified organic polycarboxylic acid, a polyhydric alcohol, and an organic polycarboxylic acid; more particularly, from a partially esterified organic polycarboxylic acid, containing a free carboxyl group, and a partially esterified polyhydric alcohol, containing an unreacted alcoholic group and obtainable by the interaction of a polyhydric alcohol with an organic polycarboxylic acid. I have found that the alkyd resinous condensation products resulting from the condensation of partially esterified organic polycarboxylic acids and polyhydric alcohols which are partially esterified by organic polycarboxylic acids have advantageous properties; for example, increased elasticity and greater flexibility than the related known products. I have furthermore found that the resinous condensapartiallyesterified halogen-substituted organic polycarboxylic acids with polyhydric alcohol-'- resulting from the condensation of (or sec-s) polycarboiwlic acid esters containing an unreacted alcoholic group, and especially those esters which also contain halogen, are particularly elastic.

In preparing the resinous condensation proddo ucts of the present invention in accordance with a preferred method of procedure, a partially esterified polyhydric alcohol may be prepared by the incomplete esteriflcation of a p lyhydrlc alcohol with an organic polycarboxylic acid, more eg particularly a halogen-substituted organic polycarboxylic acid, in accordance with the own procedure (e. g., U. S. Patent 1,098,776; and the resulting intermediate product may be heated with a partially esterified organic polycarboxyiic m acid, more particularly a halogen-containing partially esterified organic polycarboxylic acid.

ong the polyhydric alcohols which may be employed in accordance with the present invention, there may be mentioned by way of exam- 7g ple, glycerol, the polyglycerols, (e. g., diglycerol, triglycerol, etc., or mixtures of polyglycerols), glycols, (e. g., ethylene glycol, propylene glycol, butylene glycol, etc., or mixtures of glycols), polyglycols, (e. g., diethylene glycol, triethylene p glycol, etc, or'mixtures of polyglycols) penta= erythritol, mannitol, glucose, sugar, dextrine, starch, etc. Mixtures of two or more polyhydric alcohols, or of a polyhydrlc alcohol with-a monohydric alcohol may be used. 35

Among the polycarboxylic acids which may be employed in accordance with the present invention there may be mentioned, by way of example, aliphatic or aromatic polycarboxylic acids; as for example, succinic acid, malic acid, oxalic g0. acid, iumaric acid, maleic acid, malonic acid, sebacic acid, citric acid, tartaric acid,-pyro-tartaric acid, malo-malic acid, glutaric acid, phthalic acid, diphenic acid, 1.8-naphthalic acid, halogenated phthalic acids -(e. g., tetrachloro-phthalic acid), halogenated succinic acids (e. g., monochloro-succinic acid, mono-bromo-succinic acid, dichloro-succinic acid. dibromo-succinic acid, trichloro-succinic acid, tribromo-succinic acid, etc.), halogenated malic chloro-malicacid, mono-bromo-malic acid, etc.) halogenated maleic acids (e. g., mono-, or chloro-, or bromo-, maleic acids, etc.), halogenated fumaric acids, halogenated sebacic acids, halogenated citric acids, halogenated pyro-tartaric acids, halogenated malo-malic acids, halogenated glutaric' acids, halogenated adipic acids, and the like. Mixtures of two or more polycarboxylic acids also may be used.

The partially esterifled polycarbom'llc acids no acids (e. g., mono- 5 (COO),\R.

A represents a residue of a polycarboxylic acid, 12 represents an integer, and R represents kyl group, which, when n is greater than 1,

ester-acids, there may be mentioned: mono-methyl succinate, mono-ethyl succinate, mono-ethyl maleate, mono-ethyl malate, mono-isopropyl maleate, di-isopropyl citrate, diethyl-malo-malate, mono-isopropyl ester of mono-chloro-succinic acid, mono-ethyl phthalate, mono-ethyl tetra-chloro-phthalate,

tioned, with another as for example an aliphatic monoor poly-carboxylic acid (e. g., malic acid, succinic acid, fu-

g., benzoic acid, phthalic acid, cinnamic acid, salicylic acid, chlorbenzoic acid, diphenic acid, 1.8-naphthalic acid, benzoyl-benzolc acid, etc.) a natural resin or resin acid (e. g.

of the drying oils, etc.)

As illustrative embodiments of a manner in which the my ntion may be practiced the following examples are presented.

Example 1.A mixture of with about hydride 183 parts 01' glycerol 355 parts of mono-bromo-maleic an- BrO-CO 0 Halo is slowly heated with stirring. As the heating progresses, the mixture at first becomes 319mggeneous and then gradually increases in viscosity, while gentle distillation takes .place.

of monochloro-succinic acid (having the probable formula CH: Hz -COOH di-ester by means of caustic alkali in the known manner). The resulting mixture is further heated at about 180 to 290 C. until a sample on cooling forms a solid mass soluble in acetone. The

resulting product is a resinous material of very uble in acetone. This product, which is highly elastic, may be further heated to form a harder, less fusible and less soluble, tough, elastic resin.

It will be realized that the to the above specific examples but may be varied the greater ease of control of the reaction at the lower temperatures.

densation product.

The proportions in which the reacting materials are employed may be varied within wide limits, in the preparation of the intermediate condensation'product, the poiyhydric alcohol preferably may be employed in an amount relative to the carboxylic acid to provide a product .which con-.

tains an unreactedalcoholic group. The amount of ester-acid employed to complete the esteriflcation may be varied, depending upon the properties desired 0! the final product; the greater the proportion of ester-acid employed relative to the intermediate condensation product, the more flexible and fusible will be the resulting final product. I r

The preparation of resinous products 0! the present invention is not limited to the methods or procedure hereinbefore described, but other suitable methods or preparation may be employed.

The various resins included within the scope oi the invention are not limited to the uses above indicated but may be applied for various purposes,

the uses of the individual resins being dependent.

upon the particular properties or said individual resins, as will be evident to those familiar with the subject. Thus, a resin of a suitable rusibility and solubility may be employed either as such or in solution for the preparation of varnishes; baking enamels; paints; lacquers; adhesives; cements; impregnating, indurating, and the like compositions; molding and related plastic compositions; celluloid substitutes; stencil-paper; insulating compositions; phonograph and similar records; films; threads; enameled wire and metal plate; fioor and roof coverings; abrasive manuiactures; laminated fabric boards; and the like.

The resins also may be employed, where desirable in compositions including other materials, as for example, other resins (such as, artificial resins; e. g., the phenol-formaldehyde resins, other alkyd resins, phenol-iuriural resins, furiural-aniline resins, aldehyde-ketone resins, aldehyde-amine resins, suliur resins, etc.; the natural resins, e. g., colophony, shellac, copal, dammar, Kauri, Congo, etc.; resinous substances of the rubber type, e. g., rubber, gutta-percha, ballata, etc.; and the like); cellulose compounds (such as, nitrocellulose, cehulose ethers, and cellulose esters); plasticizing, fiexibilizing, and similar compounds (such as, camphor, caster-oil, glycerine, naphthalene, anthracene, chlor=naphtha-.

cheapening compositions (such as, pitch, asphalt,.

stearlne pitch, gilsonite, etc); fillers and other inert solid materials (such as, asbestos, sand, clay, talc, mica, hardened resins, wood flour, rotten stone, cotton, etc); suitablesolvents; or mixtures of the above or similar compositions.

In preparing mixed compositions p! the resins or the present invention and other artificial resins (as for example, those above mentioned) the resins may be mixed in the intermediate stages of their formation and the mixture may be heated to produce a complex resinous composition; thus, a fusible and soluble resin 0! the present invention may be mixed with a stage-A phenol formaldehyde resin, and the mixture may be heated to eilfect further condensation.

Inasmuch as in the preparation of the resinous products or the invention the anhydrides of the acids above mentioned may be employed alternatively or in admixture with the organic acids, it will be understood that where above or in the claims the acid is referred to. both the acid and the anhydride are intended to be included.

Since, in carrying out the above process, changes may be made without departing irom the &

scope of the invention, it is intended that all matter contained-in the above description shall be interpreted as illustrative and not in a limit ing sense, except as limited by the claims.

I claim:

1. A resinous condensation product derived from a polyhydric alcohol, 'an organic po1ycar=, boxylic acid, and a partially esterifled organic poiycarboxylic acid.

2. A resinous condensation product derived from a Kpolyhydricalcohol. an organic polycarboxylic acid, and a partially esterifled halogensubstituted organic polycarboxylic acid.

3. A resinous condensation product derived from the reaction oi. a polyhydric alcohol with a halogen-substituted organic polycarboxylic acid in an amount insuflicient completely to esterii'y all of said polyhydric alcohol, and with a partially esterifled organic polycarboxylic acid.

4. A resinous condensation product derived from the reaction of a polyhydric alcohol with a a halogen-substituted organic polycarboxylic acid acid and a polyhydric alcohol which is partially 110 esterifled by an organic polycarboxylic acid.

'7. A resinous condensation product derived from a polycarboxylic acid partially esterifled by an alcohol, and a polyhydric alcohol partially esterifled by a polycarboxylic acid difierent from 1 5 the first mentioned acid.

8. A resinous condensation product derived from a polyhydric alcohol partially esterifled by a polycarboxylic acid, and a polycarboxylic acid partially esterifled by a polyhydrlc alcohol dif- 12o ierent from the first mentioned alcohol.

9. A resinous condensation product derived from a partially esterifled organic polycarboxylio acid and a polyhydric alcohol which is partially esterifled by a halogen-substituted organic polycarboxylic acid.

10. A resinous condensation product derived rrorn a partially esterifled halogen-substituted aliphatic dicarboxylic acid and a polyhydric alcohol which is partially esterifled by a halogen- 13 substituted organic polycarboxylic acid.

11. Aresinous condensation product derived from a partially esterifled organic polycarboxylic acid and an organic polycarboxylic acid ester of glycerol, which ester contains a free alcoholic group.

12. A resinous condensation product derived from a partially esterifled halogen-substituted organic polycarboxylic acid and a. glycerol ester of a halogen-substituted aliphatic carboxylic acid, which ester contains a tree alcoholic group.

1 13. A resinous condensation product derived from a partially esterifled organic polycarboxylic acid and a mono-chloro-maleic acid esteror glycerol, which ester contains a i'ree alcoholic group.

14. A resinous condensation product derived from mono-isopropyl ester' oi-.mono-chloro-succinic acid and a mono-chloro-maleic acid ester of glycerol, which ester contains a tree alcoholic roup, we

15. A process of producing resinous condensation products which comprises heating a polytion products which comprises heating a polyhydric alcohol with an organic polycarboxylic acid in an amount insufiicient completely to esterify all of said polyhydric alcohol and with mono-isopropyl ester of mono-chloro-succinic acid.

18. A process of producing resinous condensation products which comprises heating a polyhydric alcohol with a halogen-substituted aliphatic polycarboxylic acid in an amount insufllcient completely to esterify all of said polyhydric alcohol and with a partially esterifled aliphatic polycarboxylic acid.

19. A process of producing resinous condensation products which comprises heating a polyhydric alcohol with a halogen-substituted aliphatic polycarboxylic acid in an amount insuflicient completely to esterity all of said polyhydric alcohol and with a partially esterified halogen-substituted organic polycarboxylic acid.

20.. A process of producing resinous condensation products which comprises heating a polyhydric alcohol with an organic polycarboxylic acid in an amount insuflicient completely to esterify all of said polyhydric alcohol and heating the resulting partially esterifled polyhydric alcohol with a partially esterifled aliphatic polycarboxylic acid.

21. A process of producing resinous condensation products which comprises heating glycerol with a halogen-substituted aliphatic polycarbox ylic acid in an amount insufllcient completely to esterify all of said glycerol and heating the resulting partially esterifled glycerol with a partially estcrified halogen-substituted organic polycarboxylic acid.

22. A process oLproducing resinous condensation products which comprises heating glycerol with mono-chloro-maleic acid in an amount insufllcient completely to esteriiy all of said glycerol and heating the resulting partially esterifled glycerol with mono-isopropyl ester of mono-chloro-succinic acid.

FRITHJOF ZWILGMEYER. 

